Novel resinous material by reaction of epoxy compounds and polyglutamic acid salts

ABSTRACT

A method for preparing a novel compound, i.e. a resinous material, characterized in that an epoxy compound is allowed to react with ammonium salt or a metal salt (for example, lithium salt, sodium salt, potassium salt, magnesium salt, etc.) of polyglutamic acid. The resulting reaction product is useful in a method for treating shaped materials especially polyester textiles. In this method the shaped materials are treated with the novel resinous material to improve the appearance and handling characteristics thereof. A process for providing a wooly finish on polyester textiles is characterized by treating textiles (including polyester knittings and mixed spun fabrics or knittings or mixed woven fabrics or knittings) in a bath of an emulsified mixed solution of an epoxy compound and a metal salt of polyglutamic acid containing a catalyst, and carrying out a heat-treatment of the resulted textiles after pre-drying.

The present invention relates to a method for preparing a novel resinousmaterial which is a reaction product obtained by allowing an epoxycompound to react with a water soluble salt of polyglutamic acid such asammonium salt and metal salts thereof (including lithium, sodium,potassium, magnesium salts and the like.) (The salts of polyglutamicacid will be hereinafter referred to as PGS.) The structure of the novelreaction product or compound obtained by allowing an epoxy compound toreact with PGS has not yet been clarified in detail. However, it hasbeen found that this product has quite different properties from thoseof both of the starting materials.

In accordance with the present invention the PGS used is soluble inwater. On the other hand, most of epoxy compounds are insoluble inwater. When a water soluble epoxy compound is employed, the compound isdissolved in water. When a water insoluble epoxy compound is employed,the compound is dissolved in a small amount of a hydrophobic organicsolvent or in an amount of a hydrophilic organic solvent several timesgreater than the amount of the epoxy compound, and then a suitablesurfactant is added to the thus obtained solution. Either solution ofthe epoxy compound prepared as noted above is added to an aqueoussolution of PGS to obtain an emulsion. A conventional catalyst forcuring an epoxy resin such as an amine (which will be hereinafterreferred to simply as a catalyst) is added to the emulsion and then theemulsion is subjected to reaction, if necessary with heating up to about80°C, to partially convert the emulsion into a polymer having a lowdegree of polymerization, that is, a prepolymer. Suitable reaction timeis several minutes, i.e. about 3 minutes to about 24 hours, butpreferably within the pot life time of the epoxy compound, i.e. about 12hours. Immediately after the reaction is completed, the mixture isquickly concentrated to dryness at 80°C or less. The resulted product isheated, if necessary, at 70°C to 90°C for several minutes for pre-dryingand then heated for 1 to 10 minutes. The thus obtained white or paleyellow resinous material, which absorbs water and exhibits much swellingis found to be a quite novel compound or reaction product which isinsoluble in water and common organic solvents.

Further, it has been found that the novel compound of the presentinvention can be utilized widely, for example, for treating orprocessing paper, natural leather, textiles including natural,artificial and synthetic fabrics, knitted good, thread, yarn, fiber andunwoven cloth, etc. to provide the materials with excellent touch andfeel. For example, in the case wherein the novel compound is applied toa fabric as a treating agent, feel of the fabric is much improved. Moreparticularly, the fabric is steeped in an emulsion containing asurfactant, an epoxy compound, PGS and a catalyst and, after theemulsion is swished off, the fabric is subjected to pre-drying at 70°C -90°C and thereafter to baking at 150°C for several minutes. The obtainedfabric is subjected to soaping sufficiently with 0.5 % aqueous solutionof Marseille soap, washed with water thoroughly and ironed afterswishing water off and air-drying. The thus treated fabric is found tobe remarkably improved in feel or handle when compared with anon-treated one.

Thus it will be appreciated that many attempts have been made to developa method for processing polyester fabrics to have a soft, warm andvoluminous feeling possessed by pure wool fabrics in order to applypolyester fabrics for outergarments which have been manufacturedexclusively of wool. The present invention can provide textiles with afeel and a resistance to wrinkling equivalent or superior to those ofwool fabrics by treating the textiles with the novel compound, i.e. oneformed by the reaction of an epoxy compound and a metal salt ofpolyglutamic acid. As heretofore noted, the chemical structure of thenovel compound has been still unknown. However, a metal salt ofpolyglutamic acid, for example, sodium salt of polyglutamic acid, can beconsidered appropriate as a material for wooly finish, because thepolypeptide structure of its main chain resembles the structure of woolitself, as shown by the general formula: ##EQU1## (wherein n is apositive integer of from 15 to 3,500)

The reaction of sodium salt of polyglutamic acid and an epoxy compoundin the presence of a catalyst is considered to be a cross-linkingreaction in which opening of epoxy rings takes part, and therefore thereaction product provides textiles with an elastic resilience, softness,a resistance to washing and a resistance to dry cleaning.

By the following procedure, it is confirmed that other reactions thanthe above-mentioned reaction do not occur on the treated fabric. Thesimilar operations as in the present invention, in which the combinationof PGS, epoxy compound, surfactant and catalyst is employed, are carriedout while using the five combinations of:

1.

surfactant,

epoxy compound, and

catalyst

2.

Pgs and

catalyst

3.

catalyst

4.

Pgs

surfactant, and

catalyst

5.

sodium glutamate

epoxy compound

surfactant, and

catalyst

The obtained products are investigated on properties and chemicalstructures by the infra-red absorption spectrum analysis and the like.As a result, the novel compound which swells in water is found to beproduced only when a combination of PGS, epoxy compound, surfactant andcatalyst is used. Further, the similar fabrics as mentioned above aresteeped in the above-mentioned five kinds of reaction solutions andsubjected to drying, baking, soaping, washing and final drying, and thenthe treated fabrics are examined for feel or handle. As a result, it isfound that those fabrics are harder in touch or remarkably inferior infeel when compared with the fabrics treated with the solution consistingof PGS, epoxy compound, surfactant and catalyst.

The water soluble ammonium or metal salts of polyglutamic acid abovedescribed and employed in the present invention may be either opticallyactive or inactive.

Usually, such a salt is obtained by saponifying poly-γ-alkylglutamatewith alcohol, aqueous alcohol or the like containing lithium hydroxide,potassium hydroxide, sodium hydroxide or the like and, if necessary theresultant product is converted to a desired form of salt such asammonium salt, lithium salt, sodium salt, potassium salt, magnesium saltor the like by a suitable method. Alternatively, polyglutamic acid isproduced by polymerizing directly glutamic acid by heating or bypolymerizing glutamic N-carboxylic anhydride obtained by reactingglutamic acid with phosgene in an organic solvent, and the polyglutamicacid is converted into ammonium salt or a metal salt (lithium salt,sodium salt, potassium salt, magnesium salt, etc.) In general, thepolymer, i.e. the polyglutamic acid has a molecular weight of from 2,000to 500,000.

As an epoxy compound used in the present invention, any compounds havingat least one vicinal epoxy group in the molecule are usable. Thecondensates of alcohol-compounds or phenol-compounds withepichlorohydrin or β-methyl epichlorohydrin are the examples of thosecommonly on the market, for example:

1. A compound having the general formula (I): ##SPC1##

wherein n is an integer of 0 to 15.

2. A compound of halogenated bisphenol type having the general formula(II): ##SPC2##

wherein X represents a halogen atom.

3. A compound of resorcin type having the formula (III): ##SPC3##

4. A compound of bisphenol F type having the formula (IV): ##SPC4##

5. A compound of tetrahydrophenylethane type having the formula (V):##SPC5##

6. A compound of novolac type having the formula (VI): ##SPC6##

wherein n is an integer of 0 to 2.

7. A compound of oxyalkylene glycol type having the formula (VII):##EQU2## wherein R represents a hydrogen atom or an alkyl group(containing from 1 to 20 carbon atoms), and n is an integer of 1 to 20.

8. A compound of glycerin-triether type,1,2,3-tris(2,3-epoxy-propoxy)propane, having the formula (VIII):##EQU3##

9. A compound of poly olefin type having the formula (IX): ##EQU4##wherein R represents a hydrogen atom or an alkyl group of from 1 to 20carbon atoms.

Further, soybean oil epoxide or alicyclic type compound such as vinylcyclohexene dioxide, etc. may be also used as an epoxy compound.

As to process of treating textiles, it has been found that particularlyeffective results are obtained when the epoxy compound is a condensateof a phenolic compound or alcoholic compound with epichlorohydrin orβ-methyl-epichloro-hydrin.

The epoxy compound used in preparation of a treating solution fortextiles is substantially insoluble in water and required to beemulsified in an aqueous solution to use in the present invention. Forthis purpose, a solvent capable of readily dissolving the epoxy compoundand an emulsifier is used. Usually, aromatic hydrocarbons such asbenzene, toluene, xylene, etc., and ketones such as acetone,methylisobutylketone, methyl ethyl ketone, etc. are used. Appropriateemulsifiers used in this aspect of the present invention aresurfactants, preferably non-ionic or cationic surfactants.

As the catalyst, any conventional catalysts employed in the productionof an epoxy resin, for example, mono- or di-amines such as dibutylamine,propylamine, isopropylamine, n-butylamine, isobutylamine, modifiedpolyamine compounds [for example, Epomate F-100 (trade name) produced byAjinomoto Co.] and ammonium salts such as ammonium borofluoride (NH₄BF₄) and ammonium sulfamate; metal salts such as zinc borofluoride[Zn(BF₄)₂ ], sodium thiosulfate (Na₂ S₂ O₃) and potassium thiocyanate(KSCN); amine salts such as C₂ H₅ NH₃ ^(+BF) ₄ ⁻ and C₆ H₁₁ NH₃ ^(+BF) ₄^(-;) organic acids or anhydrides thereof, etc. may be used. For theprocess of treating polyester textiles those catalysts having activehydrogen groups such as amines are preferred.

An epoxy compound, a material of the present invention is substantiallyinsoluble or hardly soluble in water. Therefore, the compound isnecessarily emulsified in an aqueous solution of PGS. The organicsolvents to be employed are preferably those hydrophobic and capable ofeasily dissolving epoxy compounds and surfactants. Usually, aromatichydrocarbons such as benzene, toluene, xylene, etc. and ketones such asacetone, methylisobutylketone, methylethylketone are used.

As for the surfactant used in the present process, there is noparticular limitation. Any surfactants usually used for emulsifying anepoxy compound may be employed. Examples of these surfactants arecationic surfactants such as poly-oxyethylene alkyl amine typesurfactants (for example, polyethylene lauryl amine) and quaternaryammonium salt type surfactants (for example, lauryltrimethyl ammoniumchloride); and non-ionic surfactants such as polyoxyethylene alkylethertype surfactants (for example, polyoxyethylene laurylether andpolyoxyethylene oleylether), polyoxyethylene alkylphenol ether typesurfactants (for example, octylphenol ether), polyoxyethylene acylethertype surfactants (for example, polyethylene glycol monolaurate) andsorbitan fatty acid ester (for example, sorbitan monolaurate). When anepoxy compound is allowed to react with the solution of PGS withoutusing a surfactant, the reaction does not proceed well.

It has been found that when a textile mainly consisting of polyesterfibers is treated with the novel compound of the present invention,touch of the textile is remarkably improved as that of wool and furtherwhen other textiles are treated as above, they show respectivelycharacteristic improved feel or handle.

In the present process, non-volatile matters (epoxy compound, PGS andcatalyst) are usually used in a total amount up to 0.5 - 20 % by weightof the emulsion. The mixing ratio of the epoxy compound and PGS is notparticularly limited, but usually from about 1 - 100 parts by weight ofthe epoxy compound is reacted with from about 1 - 100 parts by weight ofthe PGS. The surfactant is usually used in an amount of 1 - 20 % byweight based on the weight of the solution of the epoxy compound. Thecatalyst is used in an amount of 0.1 - 100 % by weight based on theweight of the epoxy compound.

The present invention is illustrated by the following Examples but notlimited thereby.

EXAMPLE 1

2.4 g of sodium salt of poly-L-glutamic acid [which will be hereinafterreferred to as PSLG, and has a molecular weight of 35,000 and a reducedviscosity of 1.2 (which is measured at 20°C. after dissolving the PSLGin a 0.2 mol aqueous solution of sodium chloride, and the viscositiesmentioned hereinafter are measured in the same manner as above.)] isdissolved in 320 ml of water. To said aqueous solution, the solutionprepared by dissolving 2.4 g of Epikote 812, an epoxy compound (tradename, produced by Shell Chemical Co., U.S.A., a glycerin triether typeepoxy compound having a mean molecular weight of about 306) and 0.4 g ofEmulgen-420, a surfactant (trade name, produced by Kao Soap Co., Ltd.,polyoxyethylene oleyl ether) in 5.2 g of o-xylene is added with stirringto obtain a white emulsion. To the resultant emulsion, 40 g of anaqueous solution prepared by diluting a 45% aqueous solution of zincborofluoride by 50 times with water is added dropwise for severalminutes. The obtained solution is further diluted with water up to thetotal volume of 400 ml and thereafter divided into two portions.

One part of the solution is quickly evaporated to dryness in a rotaryevaporator at a temperature below 50°C. to obtain 3.4 g of a milk-whitesolid. The solid is placed on a Petri dish and heated for pre-drying at80°C. for about five minutes and then subjected to curing at 150°C. forthree minutes, whereby 2.9 g of a milk-white solid is obtained. 200 mlof water is added to the obtained solid. The mixture is stirred for 30minutes at room temperature. The insoluble is separated by filtration toobtain 1.2 g (weight in the dry state) of white water-insoluble flakeshaving a smooth surface and a water-swelling property. The white flakeswhich are insoluble but swell in water show an infra-red spectrumdifferent from any of the infra-red spectra of the starting materials,therefore are assumed to be a novel compound consisting of PSLG and theepoxy compound. The resulting novel product is substantially insolublein solvents such as water, alcohol, acetone, N,N-dimethylformamide,dimethylsulphoxide and chloroform. Thus, the product is different insuch a character from the starting materials. Further, the product isinsoluble also in toluene, xylene, etc.

From the filtrate, 1.2 g of white powders as well as a transparent oilis obtained by distilling off water in a rotary evaporator.

On the other hand, a test piece of each of: (1) rayon taffeta, (2) nylontaffeta, (3) acetate taffeta, (4) acryl knit, (5) combed-wool fabric,(6) polyester-wool fabric (4:6), (7) polyester-rayon fabric (4:6) and(8) polyester-cotton fabric (4:6) [the ratios in the parentheses aremixing ratios of the materials] is steeped in another portion of theemulsion for several minutes and, after the emulsion is lightly swishedoff, subjected to pre-drying at about 80°C. for 5 minutes. The thustreated test piece is subjected to curing at about 150°C. for 3 minutesafter air-drying. Then the piece is subjected to soaping in 0.5% aqueoussolution of Marseille soap and, after the solution is swished off,washed thoroughly with water, and finally air-dried and then ironed. Allof the thus treated fabrics have more excellent touch and feel whencompared with the non-treated ones or those treated with the treatingagent on the market.

FIG. 1 shows an infra-red absorption spectrum of the novel compoundobtained in Example 1 measured by the KBr tablet method.

EXAMPLE 2

A reaction is carried out in the same manner as in Example 1 using 2.7 gof potassium salt of poly-D-glutamic acid (having a reduced viscosity of1.1) in place of PSLG employed in Example 1, 2.4 g of Epikote 812, 5.2 gof o-xylene, 0.4 g of Emulgen 420 and 33.6 g of 1% solution oftriethylene tetramine in place of zinc borofluoride, whereby is obtained1.0 g of the same water insoluble compound as in Example 1.

Further, the same treatment as in Example 1 is carried out on thefabrics to obtain those having good feel.

EXAMPLE 3

Procedures of Example 1 are repeated using ammonium sulfamate in placeof zinc borofluoride. 1.2 g of a similar novel compound is obtained. Thefabrics treated in the same manner show a touch of good feel.

EXAMPLE 4

2.4 g of lithium salt of poly-L-glutamic acid (which will be hereinafterreferred to as PLLG, and has a reduced viscosity of 1.1), 2.4 g ofEpikote 828, an epoxy compound (trade name, produced by Shell ChemicalCo., U.S.A., a condensate of epichlorohydrin and bisphenol A and havinga mean molecular weight of about 380), 5.2 g of o-xylene, 0.4 g ofEmulgen-420 and 33.6 g of 1% solution of triethylenetetramine are mixed,and divided into two portions. One portion is subjected to curing at160°C. for about 6 minutes, whereby 0.8 g of a water insoluble novelcompound is obtained.

Test pieces of the fabrics are steeped in the other portion of themixture and treated in the same manner as in Example 1 to obtain thefabrics having good feel.

EXAMPLE 5

Procedures of Example 4 are repeated by using ammonium or magnesium saltof polyglutamic acid in place of PLLG, and zinc borofluoride or ammoniumsulfamate as a catalyst, whereby the similar results are obtained.

EXAMPLE 6

2.4 g of PSLG, 0.4 g of Emulgen-420, 5.2 g of o-xylene and 40 g of thedilute solution obtained by diluting 45% aqueous solution of zincborofluoride 50 times with water are mixed (no epoxy compound isemployed). The mixture is divided into two portions. One portion of themixture is subjected to a reaction and the dried-up reaction product isfurther subjected to curing by heating. The resultant final product iseasily soluble in water. Further, the fabrics treated in the similarmanner as in Example 1 using the other portion of the mixture are hardin touch and accordingly remarkably inferior to the fabrics obtained inExample 1.

EXAMPLE 7

The same reaction as in Example 1 is carried out except PSLG isexcluded, and the final product obtained after heat curing, is watersoluble, transparent and heavily syrupy, different from the product inExample 1.

Further, the fabrics treated with the emulsion are remarkably inferiorin feel to those of Example 1.

EXAMPLE 8

The same reaction as in Example 1 is carried out except 2.4 g of sodiumL-glutamate is used in place of PSLG, Different from the case in Example1, a water soluble solid and a transparent heavy syrup are obtained asthe final products after heat curing.

Further, the fabrics are treated in the same manner as in Example 1 witha half of the emulsion obtained according to the above, but the thusobtained fabrics are inferior in feel to those of Example 1.

EXAMPLE 9

An emulsion is produced using PSLG, Epikote 812, Emulgen-420 and zincborofluoride in the same manner as in Example 1. Test pieces of thefabrics, i.e. (1) all polyester filament fabric, (2) spunpolyester-rayon fabric (6:4), (3) polyester-wool (6:4), (4) spunpolyester fabric and (5) polyester-cotton fabric (7:3) are steeped inthe obtained emulsion and treated in the same manner as in Example 1.All of the thus treated fabrics are found to be provided with such touchand feel as those of woolen fabrics and to be more excellent in saidproperties than the non-treated fabrics.

EXAMPLE 10

Test pieces of various polyester fabrics of Example 9 are treated withthe emulsions of Examples 2 and 3 to obtain the fabrics having excellenttouch and feel. The thus treated fabrics are superior to the non-treatedones.

EXAMPLE 11

Test pieces of various polyester fabrics of Example 9 are treated withthe emulsion of Example 4. Thereby, are obtained the fabrics having muchmore excellent feel than the non-treated ones.

EXAMPLE 12

Test pieces of various polyester fabrics of Example 9 are treated withthe emulsion of Example 4 except ammonium salt of polyglutamic acid ormagnesium salt of polyglutamic acid is used in place of PLLG, and zincborofluoride or ammonium sulfamate is used as a catalyst. The fabricsexcellent in feel are obtained as in Example 11.

EXAMPLE 13

Various polyester fabrics of Example 9 are treated with the emulsion ofExample 6. The thus treated fabrics are hard in touch and remarkablyinferior in feel to the fabrics of Example 9.

EXAMPLE 14

Various polyester fabrics of Example 9 are treated with the emulsion ofExample 7. The thus treated fabrics are remarkably inferior in feel tothe fabrics of Example 9.

EXAMPLE 15

Various polyester fabrics of Example 9 are treated with the emulsion ofExample 8. The thus treated fabrics are inferior in feel to the fabricsof Example 9.

EXAMPLE 16

Procedures of each of Examples 1 and 9 are repeated using Ameet 105(trade name, produced by Kao Soap Co. Ltd., chemical name:polyoxyethylene alkylamine) in place of Emulgen-420, a surfactant.Similar results are obtained.

EXAMPLE 17

Procedures of each of Examples 1 and 9 are repeated using Emunone 1112(trade name, produced by Kao Soap Co. Ltd., chemical name: polyethyleneglycol monolaurate) in place of Emulgen-420, a surfactant. Similarresults are obtained.

EXAMPLE 18

Procedures of each of Examples 1 and 9 are repeated using Emel A (tradename, produced by Kao Soap Co., Ltd., chemical name: ammonium salt oflauryl sulphate) is used in place of Emulgen-420, a surfactant. Similarresults are obtained.

EXAMPLE 19

Sodium salt of polyglutamic acid (intrinsic viscosity: 1.01, molecularweight: about 48,000, measured in 0.2M aqueous solution of sodiumchloride at 25°C.), epoxy compound [Epikote 828 (phenolic epoxycompound) made by Shell Chemical Co.] and catalysts of (a) diamine(Epomate F-100, made by Ajinomoto Co.), (b) 45% aqueous solution of zincborofluoride (made by Hashimoto Kasei Co.) and (c) ammonium sulfamate(made by Nitto Kagaku Kogyo Co.) are prepared. Epikote 828 is used inthe form of a solution of a self-emulsifiable resin which is prepared asbelow.

Preparation of a solution of self-emulsifiable Epikote 828:

30 g of Epikote 828 is weighed out, and dissolved in 65 g of xylene.Further, 5 g of an emulsifier is added thereto. Emulgen 420 (made by KaoSoap Co.) is used as the emulsifier.

The respective reagents prepared above are mixed in the proportions asshown in Table 1, and finally their total amount is made up of 1 literwith water. Thus, treating solutions are obtained.

                  Table 1                                                         ______________________________________                                        Preparation of Treating Solutions                                                         Test Run  No. 1    No. 2  No. 3                                   Treating agents                                                               ______________________________________                                        polyglutamate     3 g      3 g      3 g                                       epoxy compound    20 g     20 g     20 g                                      diamine (Epomate F-100)                                                                         4 g                                                         zinc borofluoride (45%)    4 g                                                ammonium sulfamate                  4 g                                       ______________________________________                                    

Of course, the respective water-soluble reagents (for example,glutamate, diamine, etc.) may be allowed to be aqueous solutions inadvance and thereafter mixed according to the composition ratios asshown in Table 1.

The treating solutions as prepared above are placed in treatingbath-tubs. Polyester fabrics scoured and dried in advance are treatedunder the conditions of a bath temperature of 15 - 30°C., pH 4.5 - 10, asqueezing ratio of 50 - 80%, a pre-drying temperature of 80°C., aheat-treating temperature of 150°C. and a heat-treating time of 30 - 180seconds.

The test results are shown in Table 2.

                  Table 2                                                         ______________________________________                                        Resistance to Wrinkling                                                                            Warp   Weft                                              ______________________________________                                        Untreated cloth        87.8%    87.2%                                         Treated cloth (Test Run No. 1)                                                                       90.1%    89.5%                                         ""(Test Run No. 2)     89.5%    88.4%                                         ""(Test Run No. 3)     90.5%    89.5%                                         ______________________________________                                    

The softness obtained in Test Run No. 3 is the highest and that in TestRun No. 2 is low. In Test Run No. 3, the reaction proceeds ratherslowly. Therefore, practically the treating method of Test Run No. 1 isthe best.

EXAMPLE 20

Similar procedures as Example 19 are repeated except using sodium saltof polyglutamic acid having an intrinsic viscosity of 1.4 and amolecular weight of about 74,000 and Epikote 812 (glycerin triether typeepoxy compound, made by Shell Chemical Co.). Results as shown in Table 4are obtained. The softness is increased, as compared with the case whereEpikote 828 is used. The tendency of the resistance to wrinkling is thesame as in Example 19. The treating solutions are prepared according toTable 3.

                  Table 3                                                         ______________________________________                                        Preparation of Treating Solution                                                          Test Run  No. 4    No. 5  No. 6                                   Treating agents                                                               ______________________________________                                        polyglutamate     3 g       3 g     3 g                                       epoxy compound (Epikote 812)                                                                    20 g     20 g     20 g                                      diamine (Epomate F-100)                                                                         4 g                                                         zinc borofluoride (45%)    4 g                                                ammonium sulfamate                  4 g                                       ______________________________________                                    

                  Table 4                                                         ______________________________________                                        Resistance to Wrinkling                                                                            Warp   Weft                                              ______________________________________                                        Untreated cloth        87.8%    87.2%                                         Treated cloth (Test Run No. 4)                                                                       90.5%    90.0%                                         ""(Test Run No. 5)     89.8%    88.5%                                         ""(Test Run No. 6)     90.8%    90.0%                                         ______________________________________                                    

EXAMPLE 21

Similar procedures as in Examples 19 and 20 are repeated using potassiumsalt (reduced viscosity: 1.20), lithium salt (reduced viscosity: 1.12)or magnesium salt (reduced viscosity: 1.05) in place of sodium salt ofpolyglutamic acid. The thus treated polyester fabrics have the almostsame wooly feel as those in Examples 19 and 20.

EXAMPLE 22

Procedures of Example 1 are repeated using 2.4 g of PSLG having anintrinsic viscosity of 0.3 and 2.4 g of PSLG having an intrinsicviscosity of 2.5 in place of the PSLG of Example 1, whereby the similarresults are obtained.

EXAMPLE 23

The treating solution which has the same composition as that of Test RunNo. 1 of Example 19 but the five times higher concentration, isprepared. The same treatment as in Example 19 is repeated using the thusprepared solution under the same conditions except that the squeezingratio is 15 - 20%. Thus, the same result is obtained.

While the novel principles of the invention have been described, it willbe understood that various omissions, modifications and changes in theseprinciples may be made by one skilled in the art without departing fromthe spirit and scope of the invention.

What is claimed is:
 1. A novel resinous material which is obtained byreacting an epoxy compound which has at least two 1,2-epoxy groups witha salt selected from the group consisting of ammonium, lithium, sodium,potassium and magnesium salts of polyglutamic acid, said salt beingwater-soluble and having a molecular weight of 2,000 to 500,000.
 2. Theresinous material of claim 1, wherein said epoxy compound is selectedfrom the group consisting of glycidyl ethers of bisphenol A, resorcinol,bisphenol F, fetrakis-(hydroxyphenyl)ethane type, novolacs, oxyalkyleneglycols, glycerol or a, polyolefin and alicyclic epoxy compounds andsoybean oil epoxides, said epoxy compound consisting of carbon, hydrogenand oxygen.
 3. The resinous material of claim 1, wherein said epoxycompound is a glycidyl ether of a halogenated bisphenol consisting ofcarbon, hydrogen, oxygen and halogen.
 4. The resinous material of claim1, wherein said epoxy compound is selected from the group consisting of:##SPC7##wherein n is an integer of 0 to 15; ##SPC8## wherein Xrepresents a halogen atom; ##SPC9## ##SPC10## wherein n is an integer of0 to 2; ##EQU5## wherein R represents a hydrogen atom or an alkyl having1 to 20 carbon atoms, and n is an integer of 1 to 20; ##EQU6## wherein Rrepresents a hydrogen atom or an alkyl having 1 to 20 carbon atoms;soybean oil epoxides; and vinyl cyclohexene dioxide.
 5. A novel resinousmaterial which is obtained by a method comprising the steps of:forming asolution of an epoxy compound having at least two 1,2-epoxy groupscontaining a surfactant, mixing said solution with an aqueous solutionof a salt selected from the group consisting of ammonium, lithium,sodium, potassium and magnesium salts of polyglutamic acid which iswater-soluble and has a molecular weight of 2,000 to 500,000 to obtainan emulsion, adding a catalyst for curing epoxy resin selected from thegroup consisting of amines, ammonium salts, amine salts, metal salts,and organic acids or their anhydrides to said emulsion, reacting saidepoxy compound with said water-soluble salt of polyglutamic acid to forma resinous reaction product in said emulsion, and recovering saidreaction product from said emulsion.
 6. The resinous material of claim5, wherein from about 1 to 100 parts by weight of the epoxy compound arereacted with from about 1 to 100 parts by weight of said water solublesalt of polyglutamic acid.
 7. The resinous material of claim 5, whereinsaid solution of epoxy compound contains from about 1 to 20% by weightof said surfactant.
 8. The resinous material of claim 5, wherein about0.1 to 100% by weight of said catalyst based on the weight of the epoxycompound is admixed with said emulsion.
 9. The resinous material ofclaim 5, wherein said emulsion contains 0.5 to 20% by weight ofnon-volatile matter.
 10. The resinous material of claim 5, wherein saidsolution of epoxy compound is prepared by dissolving the epoxy compoundin water.
 11. The resinous material of claim 5, wherein the solution ofepoxy compound is obtained by dissolving the epoxy compound in ahydrophobic solvent selected from the group consisting of benzene,toluene and xylene.
 12. The resinous material of claim 5, wherein theepoxy solution is prepared by dissolving the epoxy compound in ahydrophilic organic solvent selected from the group consisting ofacetone, methyl ethyl ketone and methyl isobutyl ketone.
 13. Theresinous material of claim 5, wherein said epoxy compound is a compoundcapable of forming an epoxy resin in the presence of said catalyst. 14.The resinous material of claim 5, wherein said catalyst has activehydrogen groups.
 15. The resinous material of claim 5, wherein saidcatalyst is selected from the group consisting of dibutylamine,propylamine, isopropylamine, n-butylamine, isobutylamine, modifiedpolyamine compounds, C₂ H₅ NH₃ ^(+BF) ₄ ⁻ and C₆ H₁₁ NH₃ ^(+BF) ₄ ⁻. 16.The resinous material of claim 5, wherein said surfactant includes thosesurfactants capable of emulsifying said epoxy compound in an aqueoussystem.
 17. The resinous material of claim 5, wherein said catalyst isselected from the group consisting of ammonium borofluoride, ammoniumsulfamate, zinc borofluoride and potassium thiocyanate.
 18. The resinousmaterial of claim 5, wherein said epoxy compound is selected from thegroup consisting of glycidyl ethers of bisphenol A, resorcinol,bisphenol F, tetrakis-(hydroxyphenyl)ethane novolacs, oxyalkyleneglycols glycerol or a polyolefin and alicyclic epoxy compounds andsoybean oil epoxides, said epoxy compound consisting of carbon, hydrogenand oxygen.
 19. The resinous material of claim 5, wherein said epoxycompound is glycidyl ether or a halogenated bisphenol consisting ofcarbon, hydrogen, oxygen and halogen.
 20. The resinous material of claim5, wherein said epoxy compound is selected from the group consisting of##SPC11##wherein n is an integer of 0 to 15; ##SPC12## wherein Xrepresents a halogen atom; ##SPC13## ##SPC14## wherein n is an integerof 9 to 2; ##EQU7## wherein R represents a hydrogen atom or an alkylhaving 1 to 20 carbon atoms, and n is an integer of 1 to 20; ##EQU8##wherein R represents a hydrogen atom or an alkyl having 1 to 20 carbonatoms; soybean oil epoxides; and vinyl cyclohexene dioxide.